A theoretical study describing primary electron backscattering from solids and double layers is presented. The analysis involves a novel and illuminating extension of Everhart’s theory to obtain the dependence of backscattering coefficient on both retarding potential energy and double‐layer target thickness. For solid targets, energy distribution spectra are calculated with the atomic number of the target material as a parameter and are compared with existing experiments to show good agreement. The backscatteringanalysis for double‐layer targets is particularly interesting in that pronounced structure is predicted from the calculated energy distribution spectra due to the assumed discontinuous change in target atomic number across the interface. Comparison of calculated and experimentally obtained backscattering coefficients for double‐layer targets and supported thin films also indicate reasonable agreement.